Superabsorbent polymers having delayed water absorption characteristics

ABSTRACT

A superabsorbent polymer comprising a delayed absorption superabsorbent polymer having a free water absorbency property of absorbing less than about 3 grams of aqueous saline per gram of superabsorbent polymer in about 6 seconds, for a full particle size distribution of superabsorbent polymer ranging from about 40 micrometers to about 890 micrometers.

This is a Divisional Application that claims priority to U.S.application Ser. No. 09/602,852 filed Jun. 26, 2000 now U.S. Pat. No.6,514,615 and Provisional Application Ser. No. 60/141,412 filed Jun. 29,1999.

TECHNICAL FIELD

The present invention relates, in general, to absorbent polymers thatabsorb aqueous liquids (such as water, blood, and urine). Moreparticularly, the present invention relates to superabsorbent polymers,namely polymers that absorb over 100 times their weight in water, whichsuperabsorbent polymers have unique characteristics of delayed waterabsorption, and a novel method for making such superabsorbent polymers.As is well known, superabsorbent polymers have many uses, particularlyin absorbent sanitary articles, such as disposable diapers, disposableadult incontinence garments, disposable sanitary napkins, and disposablebandages. The superabsorbent polymers of the present invention, due totheir delayed water absorption characteristics, are particularly usefulin the manufacture of a web of superabsorbent polymer and cellulosicfiber for use as a core composite in such sanitary articles, when theweb is made by the wet-laid process.

DEFINITIONS OF ABBREVIATIONS

The following abbreviations are employed throughout this specification.

Abbreviation Definition AUL absorbency under load All-PEGMA allyloxypolyethylene glycol methacrylate, a X-linking agent cm centimeter CRCcentrifuge retention capacity X-linking cross-linking EO-TMPTAethoxylated trimethylol-propane triacrylate, a X-linking agent FWA freewater absorption mg milligram mm millimeter ppm parts per million psipounds per square inch SAP superabsorbent polymer, a polymer thatabsorbs over 50 times, more preferably over 75 times, even morepreferably over 100 times, its weight in water ABAH2,2′-azobis(2-amidino-propane) dihydrochloride, a polymerizationinitiator

BACKGROUND OF THE INVENTION

When superabsorbent technology was first developed, only a high swellingcapacity on contact of the superabsorbent polymer with liquids, referredto as the free swelling capacity in accordance with the free waterabsorption test (FWA), was the primary consideration. However, it waslater realized that the water-absorbing polymers when present in asanitary article, such as a diaper or incontinence garment, aresubjected to mechanical load caused by movements of the person wearingthe article. Thus, a new consideration arose in that the superabsorbentpolymer, in addition to having a high swelling capacity, should alsohave a high capability for retaining liquid in accordance with thecentrifuge retention capacity test (CRC) and a high absorbency underpressure in accordance with the absorbency under load test (AUL). A gooddiscussion of the test for AUL can be seen in published European PatentApplication No. 0 339 461 A1 (published Nov. 2, 1989; priority to U.S.Ser. No. 184,302 (Parent) and Ser. No. 334,260 (Continuation-in-Part),which Continuation-in-Part has issued as U.S. Pat. No. 5,147,343) toKellenberger, assignor to Kimberly-Clark Corporation.

Published European Patent Application No. 0 437 816 A1 (published Jul.24, 1991; priority to U.S. Ser. No. 464,798) to Kim and Nielsen,assignors to Hoechst Celanese Corporation, shows the wet-laid processfor the manufacture of webs of superabsorbent polymer and cellulosicfiber. These webs are employed as core composites in disposable sanitaryarticles, such as those mentioned above. More particularly, disclosed isa process that involves blending superabsorbent polymer particulateswith a liquid to form a slurry, followed by mixing cellulosic fiberswith the slurry and then filtering to remove part of the liquid, andfinally drying the resultant. The wet-laid process is also described inU.S. Pat. No. 4,605,401 (issued Aug. 12, 1986) to Chmelir and Künschner,assignors to Chemische Fabrik Stockhausen GmbH.

The journal article, “Keeping Dry with Superabsorbent Polymers”,Chemtech, (September 1994) by Buchholz, contains an excellent discussionof the conventional methods for making superabsorbent polymers, certainof which have sulfonate functional groups and certain of which havecarboxylic acid functional groups. Also, Buchholz discussed various usesfor superabsorbent polymers, such as in the above-noted sanitaryarticles, as well as in a sealing composite between concrete blocks thatmake up the wall of underwater tunnels and in tapes for water blockingin fiber optic cables and power transmission cables.

A good discussion of the methods for making superabsorbent polymers canalso be seen in U.S. Pat. No. 5,409,771 (issued Apr. 25, 1995) to Dahmenand Mertens, assignors to Chemische Fabrik Stockhausen GmbH. Morespecifically, this patent mentions that commercially availablesuperabsorbent polymers are generally cross-linked polyacrylic acids orcross-linked starch-acrylic-acid-graft-polymers, the carboxyl groups ofwhich are partially neutralized with sodium hydroxide or caustic potash.Also mentioned is that the superabsorbent polymers are made by twomethods, one being the solvent polymerization method and the other beingthe inverse suspension or emulsion polymerization method.

In the solvent polymerization method, an aqueous solution of partiallyneutralized acrylic acid for instance and a multi-functional networkcross-linking agent is converted to a gel by radical polymerization. Theresultant is dried, ground, and screened to the desired particulatesize.

On the other hand, in the inverse suspension or emulsion polymerizationmethod, an aqueous solution of partially neutralized acrylic acid forinstance is dispersed in a hydrophobic organic solvent by employingcolloids or emulsifiers. Then, the polymerization is started by radicalinitiators. Water is azeotropically removed from the reaction mixtureafter completion of the polymerization, followed by filtering and dryingthe resultant product. Network cross-linking typically is accomplishedby dissolving a polyfunctional cross-linking agent in the monomersolution.

Furthermore, U.S. Pat. No. 5,154,713 (issued Oct. 13, 1992) to Lind andU.S. Pat. No. 5,399,591 (issued Mar. 21, 1995) to Smith and Lind, bothof which patents are assigned to Nalco Chemical Company, describe newprocesses for making superabsorbent polymers, as a result of which thesuperabsorbent polymers display an increased, faster water absorption.The superabsorbent polymers are depicted as useful as absorbents forwater and/or for aqueous body fluids when the polymers are incorporatedinto absorbent structures, such as disposable diapers, adultincontinence garments, and sanitary napkins.

General background with respect to various superabsorbent polymers andmethods of manufacturing them can be seen in U.S. Pat. No. 5,229,466(issued Jul. 20, 1993) to Brehm and Mertens; U.S. Pat. No. 5,408,019(issued Apr. 18, 1995) to Mertens, Dahmen, and Brehm; and U.S. Pat. No.5,610,220 (issued Mar. 11, 1997) to Klimmek and Brehm, all of whichpatents are assigned to Chemische Fabrik Stockhausen GmbH.

The disclosures of all above-mentioned patents and published patentapplications are incorporated herein by reference.

BRIEF SUMMARY AND OBJECTS OF THE INVENTION

Accordingly, the present invention provides a delayed absorption,particulate superabsorbent polymer comprising polymeric particles havinga free water absorption property of absorbing less than about 3 grams ofwater per gram of polymeric particle in about 6 seconds, for a fullparticle size distribution from about 40 to about 890 micrometers.

Also, the present invention provides a method for making suchsuperabsorbent polymers having the free water absorption propertydescribed in the paragraph above, wherein the method comprises a firststep of preparing a particulate superabsorbent polymer by conventionalmethods, followed by a second step of subjecting the resultantparticulate polymeric particles to a two-part thermal profile.Preferably, the two-part thermal profile comprises (a) heating thepolymeric particles for about 30 to about 90 minutes at a temperaturethat increases during the heating from a beginning temperature betweenabout 50 and about 80° C. to a final temperature between about 170 andabout 220° C., followed by (b) maintaining the resultant, heatedpolymeric particles from (a) for about 30 to about 90 minutes at aconstant temperature between about 5 and about 50° C. higher than thefinal temperature of (a).

Additionally, the present invention provides a wet-laid web comprising afibrous component and a component of the delayed absorptionsuperabsorbent polymers described in the two paragraphs above.Furthermore, the present invention provides a method for improving thesolids content of a wet-laid web by making the web with the delayedabsorption superabsorbent polymers described in the two paragraphsabove.

Therefore, it is an object of the present invention to provide asuperabsorbent polymer having a decreased, slower free water absorptionas compared to prior art superabsorbent polymers of similar particulatesize, which typically have a free water absorption of more than 5 gramsof water per gram of polymeric particles at 6 seconds, often more than 7grams of water per gram of polymeric particles at 6 seconds, and incertain instances, more than 20 grams of water per gram of polymericparticles at 6 seconds.

Furthermore, it is an advantage of the present delayed absorption,superabsorbent polymers that they have not only an acceptable absorbencyunder load but also an improved solids content, as a result of whichthey are very useful in a wet-laid web of superabsorbent polymer andcellulosic fiber for use as a core composite in sanitary articles.

Moreover, it is another advantage that due to the decreased free waterabsorption property of the present superabsorbent polymers, they areparticularly useful in making a web by the wet-laid process since thedecreased free water absorption should lead to less water uptake duringthe wet-laid process of blending an aqueous slurry of superabsorbentpolymer and cellulosic fiber, which in turn, should lead to less dryingtime of the resultant web prior to placing it as a core composite in theend product, such as a disposable diaper, a disposable adultincontinence garment, or a disposable sanitary napkin.

Additionally, one more advantage is that the present superabsorbentpolymers have an ultimate free water absorption property (i.e., thetotal amount of water absorbed when the superabsorbent polymer isallowed to remain long enough, usually 3 to 5 minutes, in water until nomore water can be absorbed) that is essentially similar to that of priorart superabsorbent polymers, and consequently, the presentsuperabsorbent polymers are just as absorbent as those of the prior art.

Some of the objects and advantages of the invention having been stated,other objects and advantages will become evident as the descriptionproceeds, when taken in connection with the Laboratory Examplesdescribed below.

DETAILED DESCRIPTION OF THE INVENTION

As long as the above-mentioned two-part thermal profile is performed onparticulate superabsorbent polymer, the particulate superabsorbentpolymer may be manufactured by any of the prior art processes for makingsuperabsorbent polymers. For instance, the superabsorbent polymer may bemade by the solvent polymerization technique or may be made by theinverse suspension or emulsion polymerization technique, which are wellknown techniques as discussed above.

Thus, the superabsorbent polymer may be obtained by polymerizing atleast about 10%, more preferably about 25%, and even more preferablyabout 55 to about 99.9%, by weight of monomers havingolefinically-unsaturated carboxylic and/or sulfonic acid groups. Suchacid groups include, but are not limited to, acrylic acids, methacrylicacids, 2-acrylamido-2-methylpropane sulfonic acid, and mixtures thereof.The acid groups are present as salts, such as sodium, potassium, orammonium salts.

The acid groups are typically neutralized to at least about 25 mol %.Preferably, the extent of neutralization is to at least about 50 mol %.More particularly, the preferred superabsorbent polymer has been formedfrom cross-linked acrylic acid or methacrylic acid, which has beenneutralized to an extent of about 50 to about 80 mol %.

Additional useful monomers for making the superabsorbent polymersinclude from above 0 up to about 60% by weight of acrylamide,methacrylamide, maleic acid, maleic anhydride, esters (such ashydroxyethyl acrylate, hydroxyethylmethacrylate,hydroxypropylmethacrylate, glycidylmethacrylate, anddimethyl-aminoalkyl-methacrylate), dimethyl-aminopropyl acrylamide, andacrylamidopropyl trimethyl-ammonium chloride. Percentages below about60% of these monomers are desirable as percentages above about 60%typically will have a detrimental effect and deteriorate the swellcapacity of the resultant superabsorbent polymer.

Suitable network cross-linking agents useful in making thesuperabsorbent polymers are those which have at least two ethylenicallyunsaturated double bonds, those which have one ethylenically unsaturateddouble bond and one functional group reactive toward acid groups, andthose which have several functional groups reactive toward acid groups.Suitable kinds of network cross-linking agents include, but are notlimited to, acrylate and methacrylate of polyols (such as butanedioldiacrylate, hexanediol dimethacrylate, polyglycol diacrylate,trimethylolpropane triacrylate, tetrahydrofurfuryl-2-methacrylate,glycerol dimethacrylate, allyloxy polyethylene glycol methacrylate, andethoxylated trimethylolpropane triacrylate), allyl acrylate, diallylacrylamide, triallyl amine, diallyl ether, methylenebisacrylamide,N,N-dimethylaminoethylmethacrylate, N-dimethylaminopropylmethacrylamide, N-methylol methacrylamide, and N-methylolacrylamide.These network cross-linking agents are distinguished from and not to beconfused with the surface cross-linking agents discussed below.

Furthermore, depending on the desired end use, the superabsorbentpolymer may have a water-soluble polymeric component. The content mayrange from above 0 up to about 30% by weight of a component thatincludes, but is not limited to, partially or completely saponifiedpolyvinyl alcohol, polyvinyl pyrrolidone, starch, starch derivatives,polyglycols, polyacrylic acids, and combinations thereof. The molecularweight of the component is not critical, provided that it iswater-soluble. Preferred water-soluble polymeric components are starch,polyvinyl alcohol, and mixtures thereof. Preferably, the content of thewater-soluble polymeric component in the superabsorbent polymer rangesfrom about 1 to about 5% by weight, especially if starch and/orpolyvinyl alcohol are present as the water-soluble polymeric component.Also, the water-soluble polymeric component may be present as a graftpolymer having the acid-groups-containing polymer.

In connection with the particle shape of the superabsorbent polymer,there are no specific limitations. The superabsorbent polymer may be inthe form of small spheres obtained by inverse suspension polymerization,or in the form of irregularly shaped particles obtained by drying andpulverizing the gel mass obtained by solvent polymerization. A typicalparticle size distribution ranges between about 20 and about 2000micrometers, preferably between about 40 and about 890 micrometers, andmore preferably between about 90 and about 850 micrometers.

As is well known, the smaller the particle size, then the faster asuperabsorbent polymer will absorb water, and likewise, the larger theparticle size, then the slower a superabsorbent polymer will absorbwater. Hence, for the present invention, the particulate superabsorbentpolymer desirably has the larger particle sizes, especially for use inmaking a core composite by the wet-laid process. Sizes under about 30micrometers are generally unsuitable for the wet-laid process.Nevertheless, for any given particle size, the superabsorbent polymer ofthe present invention should absorb less water in a selected amount ofseconds (i.e., exhibit a decreased, lower free water absorption) ascompared to a prior art superabsorbent polymer of essentially the sameparticle size.

In general, the prior art processing technique for the manufacture ofsuperabsorbent polymers ends with a heat treatment. This is not to beconfused with the special two-part thermal profile that is critical inconnection with manufacture of the superabsorbent polymers of thepresent invention so that they will have the desirably low free waterabsorption characteristics.

More specifically, the following is noted with respect to the two-partthermal profile required for the present invention. The heating of eachof the two parts should be sufficient and the time of each of the twoparts should be sufficient to achieve the inventive superabsorbentpolymer with the desirable free water absorption property, as describedbelow.

In the first part, after the polymeric particles have been ground andthen sieved to the appropriate, desirable size, they are heated by beingsubjected to an increasing temperature. Typically, this is a temperaturestarting at about 50° C., more preferably about 55° C., and even morepreferably about 60° C., and ending at about 170°C., more preferablyabout 190° C., and even more preferably about 220° C. Then, for thesecond part, the temperature is quickly brought to at least about 5° C.higher than the ending temperature of the first part, and maintained atthat higher temperature. Preferably, the second part constanttemperature is no more than about 50° C. higher, more preferably no morethan about 30° C. higher, and even more preferably no more than about10° C. higher than the first part ending temperature.

The heating and the time for each of part one and part two of therequired two-part temperature profile should be sufficient so that theresultant superabsorbent polymeric particles exhibit a significantlyreduced free water absorption, as compared to prior art superabsorbentpolymeric particles of substantially the same particle size. Inparticular for the inventive particulate superabsorbent polymer, theslower free water absorption at about 6 seconds should be less thanabout 3 grams of water per gram of polymer, and in many instances, isless than about 2 grams of water per gram of superabsorbent polymer.

The free water absorption of the inventive superabsorbent polymer isreferred to as delayed, reduced, or slower, as it is intended to meanthe free water absorption in a short amount of time, i.e., 6 seconds.This is distinguished from free water absorption where thesuperabsorbent polymer is allowed to absorb water until no more watercan be absorbed, which typically is 3 to 5 minutes, and is called theultimate free water absorption as a reference to the total amount ofwater absorbed regardless of how long that takes. The inventivesuperabsorbent polymers have an ultimate free water absorptionessentially the same as prior art superabsorbent polymers commerciallyused in sanitary articles.

A typical time for the first part of the temperature profile ranges fromabout 30 minutes to about 90 minutes, more preferably from about 45minutes to about 75 minutes, even more preferably from about 55 minutesto about 65 minutes, and most preferably is about 60 minutes. Shortertimes may be employed when higher temperatures are employed. The timefor the second part of the required thermal profile is, in general,about the same as that for the first part, and likewise, shorter timesmay be employed with higher temperatures.

The superabsorbent polymers according to the present invention may bemanufactured on a large scale by continuous or discontinuous processes.Furthermore, the superabsorbent polymers according to the presentinvention may be used for a wide variety of applications, for instance,sanitary articles, water-blocking tapes and sheets for wherever leakingwater is a problem (i.e., inside of fiber-optic communication cables andpower transmission cables, between concrete blocks that make up thewalls of an underwater tunnel, such as the Channel Tunnel connectingEngland and France, as mentioned in the above-noted Buchholz journalarticle), and carriers for insecticides, pesticides and/or herbicides.

When the inventive superabsorbent polymers are used to make a web thatwill be employed as a core composite in a sanitary article, the weightratio of polymer component to fibrous component in the web should becontrolled to range from about 90:10 to about 5:95. A very suitable webhas a ratio from about 35:65 to about 45:55, and more preferably has aratio of about 40:60.

Although comminuted wood pulp (i.e., cellulosic fibers, colloquiallyreferred to as fluff) is preferred to form the fibrous component of theweb for this invention, other wettable fibers such as cotton linters canbe used. Additionally, the fibrous component may be formed frommeltblown synthetic fibers such as polyethylene, polypropylene,polyesters, copolymers of polyesters and polyamides, and the like. Thefibrous component may also be formed from a mixture of wood pulp fluffand one or more of the meltblown fibers. For example, the fibrouscomponent may comprise at least about 5 weight % preferably about 10weight % synthetic polymer fibers and the remainder may comprise woodpulp fluff. The fibers of the web are generally hydrophilic or renderedhydrophilic through a surface treatment. Cellulosic fiber is preferred,a preferred one being sold under the trademark GOLDEN ISLES® by GeorgiaPacific.

Especially, the inventive superabsorbent polymers, due to their freewater absorption characteristics, are very useful in a wet-laid processfor manufacturing a wet-laid web, having a superabsorbent polymercomponent mixed with a fibrous component and useful as a core compositein a sanitary article. Examples of the wet-laid process are described inthe above-mentioned published European Patent Application No. 0 437 816A1 and U.S. Pat. No. 4,605,401. As the wet-laid process involves mixingan aqueous slurry of superabsorbent polymer with fiber, water isabsorbed during the wet-laid process. Consequently, at the end of thewet-laid process, the wet-laid web must be dried prior to placing it asa core composite in an end use article, such as a disposable diaper.

By employing the superabsorbent polymers of the present invention, lesswater should be absorbed during the wet-laid process of making a web.Thus, there should be less water to remove during drying, resulting in ashorter, drying time for the wet web, which is very advantageous in alarge scale factory production setting.

Moreover, after drying of the wet-laid web, due to the free waterabsorbency characteristics of the superabsorbent polymer, the web willhave an improved solids content, as compared to a wet-laid webcontaining prior art superabsorbent polymer. Typically, the inventivewet-laid web will have a solids content above about 18%.

Furthermore, the inventive superabsorbent polymers are well suited foruse in a web, since they typically exhibit an acceptable centrifugeretention capacity like that exhibited by prior art superabsorbentpolymers. The inventive superabsorbent polymers usually display acentrifuge retention capacity of more than about 28, often more thanabout 30, and even more than about 32 grams of aqueous saline per gramof superabsorbent polymer.

Additionally, the inventive superabsorbent polymers are well suited foruse in a web, since they typically exhibit an acceptable absorbencyunder load property, like that exhibited by prior art superabsorbentpolymers. The inventive superabsorbent polymers usually display anabsorbency under load property of more than about 13, often more thanabout 15, and even more than about 18 grams of aqueous saline per gramof superabsorbent polymer.

As is known from the above-mentioned U.S. Pat. No. 5,409,771, coating aparticulate superabsorbent polymer with an alkylene carbonate followedby heating to effect surface cross-linking improves the absorbency underload characteristics. A desirable absorbency under load property of atleast about 13 grams of aqueous saline per gram of superabsorbentpolymer is especially desirable when the end use of the superabsorbentpolymer is in a sanitary article, such as a disposable diaper, that issubjected to pressure from the person wearing the article.

Thus, the superabsorbent polymers of the present invention arepreferably coated with a surface X-linking agent prior to the inventivetwo-part thermal profile. The preferred alkylene carbonate for surfacecross-linking is ethylene carbonate.

More specifically, as described in U.S. Pat. No. 5,409,771, for coatingof particulate superabsorbent polymer with a surface X-linking agent,the polymer may be mixed with an aqueous-alcoholic solution of thealkylene carbonate surface X-linking agent. The amount of alcohol isdetermined by the solubility of the alkylene carbonate and is kept aslow as possible for technical reasons, for instance, protection againstexplosions. Suitable alcohols are methanol, ethanol, butanol, or butylglycol, as well as mixtures of these alcohols. The preferred solvent iswater which typically is used in an amount of 0.3 to 5.0% by weight,relative to particulate superabsorbent polymer. In some instances, thealkylene carbonate surface X-linking agent is dissolved in water,without any alcohol. It is also possible to apply the alkylene carbonatesurface X-linking agent from a powder mixture, for example, with aninorganic carrier material, such as SiO₂.

To achieve the desired surface X-linking properties, the alkylenecarbonate has to be distributed evenly on the particulate superabsorbentpolymer. For this purpose, mixing is effected in suitable mixers, suchas fluidized bed mixers, paddle mixers, milling rolls, ortwin-worm-mixers. It is also possible to carry out the coating of theparticulate superabsorbent polymer during one of the process steps inthe production of the particulate superabsorbent polymer. A particularlysuitable process for this purpose is the inverse suspensionpolymerization process.

According to U.S. Pat. No. 5,409,771, the thermal treatment whichfollows the coating treatment is carried out as follows. In general, thethermal treatment is at a temperature between 150 and 300° C. However,if the preferred alkylene carbonates are used, then the thermaltreatment is at a temperature between 180 and 250° C. The treatmenttemperature depends on the dwell time and the kind of alkylenecarbonate. At a temperature of 150° C., the thermal treatment is carriedout for several hours. On the other hand, at a temperature of 250° C., afew minutes, e.g., 0.5 to 5 minutes, are sufficient to achieve thedesired surface X-linking properties. The thermal treatment may becarried out in conventional dryers or ovens. Examples of dryers andovens include rotary kilns, fluidized bed dryers, disk dryers; orinfrared dryers.

In contrast to the thermal treatment in U.S. Pat. No. 5,409,771, thepresent inventive thermal treatment (whether performed without or withthe presence of a surface X-linking agent) comprises the above-describedspecial two-part thermal profile. During the first part, the temperatureis increased, and during the second part, the temperature is maintainedat a constant temperature at least about 5° C. higher, preferably nomore than about 50° C. higher, than the end temperature of the firstpart.

To characterize the superabsorbent polymers as set out in the LaboratoryExamples below (both those superabsorbent polymers of the presentinvention, as well as those comparison, superabsorbent polymers), thecentrifuge retention capacity (CRC), the absorbency under load (AUL),and the free water absorption (FWA) were measured in the followingmanner.

CRC. The SAP's retention was determined according to the tea bag testmethod and reported as an average value of two measurements.Approximately 200 mg of SAP, that have been sieved to a particle sizedistribution of 300 to 600 micrometers (not the indicated particle sizesin the Examples below), were enclosed in a tea bag and immersed in 0.9%by weight aqueous NaCl solution for 30 minutes. Then, the tea bag wascentrifuged at 1600 rpm for 3 minutes (centrifuge diameter was about 18cm) and weighed. Two tea bags without SAP were used as blanks.

Then, the CRC was calculated according to the following equation.${C\quad R\quad C} = \frac{W_{3} - W_{2} - W_{1}}{W_{1}}$where:

-   -   CRC=Retention after an immersion time of 30 minutes (g of liquid        absorbed/g of SAP)    -   W₁=Initial Weight of SAP (g)    -   W₂=Weight of the average blank tea bags (without SAP) after        centrifugation (g)    -   W₃=Weight of the tea bag with SAP after centrifugation (g)

AUL. The SAP's absorbency of a 0.9% by weight aqueous NaCl solutionunder load was determined according to the method described on page 7 ofthe above-mentioned published European Patent Application No. 0 339 461A1. An initial weight of the SAP was placed in cylinder with a sievebottom. The SAP was loaded by a piston exerting a pressure load of 60g/cm². (It is noted 60 g/cm²≈0.9 psi.)

The cylinder was subsequently placed on a Demand-Absorbency-Tester (DAT)on a glass fritted disk of 125 mm diameter, and covered by a Whatmanfilter paper #3. Then, the SAP was allowed to absorb the 0.9% NaClsolution for 1 hour. The initial weight of the SAP was approximately 160mg, which had been sieved to a particle size distribution of 300 to 600micrometers (not the indicated particle sizes in the Laboratory Examplesbelow).

After the 1 hour, the swollen SAP was re-weighed, and grams of the 0.9%NaCl solution that had been retained was calculated. The AUL of the SAPwas the grams retained.

FWA. To determine the SAP's free water absorption, a vacuum apparatuswas assembled. More specifically, a vacuum pump was attached, by Tygontubing, to a vacuum flask, atop which was positioned the bottom portionof a Buchner funnel, that was sealed properly to the flask using aone-hole rubber stopper. A magnetic stirrer was placed beside theapparatus. After assemblage of the apparatus, the vacuum pump wasengaged and allowed to stay on throughout all FWA testing.

Using a 250 ml graduated cylinder, 150 ml±1 ml of 23.0° C.±0.5° tap H₂Owas measured into a 250 ml beaker containing a 1 inch stir bar. Thebeaker of H₂O was placed on a stir plate and allowed to stir so that thecreated vortex ended approximately 2 to 3 cm from the surface of theliquid.

A dry, 80 mesh (180 micrometer) sieve was tared on a top loadingbalance, and then placed atop the Buchner funnel and tightly anchoredthrough suction. The SAP was then weighed on a separate balance in theamount needed for the particular test: the 30 second FWA determinationemployed 1 gram of SAP, while the 15 second and the 6 seconddeterminations each employed 3 grams of SAP. The SAP was poured into thebeaker of H₂O, while simultaneously a stopwatch was started to counttime from 0. When the SAP was poured into the tap H₂O, dispersion of thediscrete particles was immediate and complete in that no discreteparticles tended to clump or aggregate.

Upon reaching the number of seconds desired, the beaker contents werepoured into a sieve, with a transfer time of no greater than 3additional seconds. The sieve was left under the vacuum forapproximately 30 additional seconds. The sieve was then removed from theBuchner funnel, and wiped on its bottom surface of mesh to remove anyresidual H₂O. The dried sieve was then placed onto a previously taredbalance and the “Gel Weight” recorded.

Then, the FWA (g of liquid absorbed/g of SAP) was calculated from thegel weight according to the following equation.${F\quad W\quad A\quad\left( {g/g} \right)} = \frac{\quad{{g\quad{Gel}\quad{Weight}} - {g\quad{Superabsorbent}}}}{g\quad{Superabsorbent}}$

LABORATORY EXAMPLES I. Comparison Examples (of Commercially AvailableSAPs) Example A

Various commercially available, prior art superabsorbent polymers weretested for FWA, CRC, and AUL. For the FWA test, each of the prior artsuperabsorbent polymers was tested at 27° C. at 750 rpm agitation speed,and had a full particle size distribution of 44 to 841 micrometers. Forthe CRC test and the AUL test, each of the prior art superabsorbentpolymers was sieved so that tested was the above-noted particle sizedistribution of 300 to 600 micrometers. The FWA test was conducted withwater, whereas each of the CRC test and the AUL test was conducted with0.9% by weight aqueous saline. The results are summarized below in TableIA.

TABLE IA Prior Art SAP and 6 15 30 Supplier seconds seconds seconds CRCAUL Company FWA (g/g) FWA (g/g) FWA (g/g) (g/g) (g/g) IM-4510 23.7 31.759.1 32.6 21.0 from Hoechst Celanese ASAP- 7.6 12.3 31.7 32.2 21.5 2300from Chemdal Sumitomo- 10.8 20.8 50.9 36.9 9.6 60S from SumitomoSalSorb- 8.9 14.8 23.1 36.5 11.9 CL20 from Allied Chemical FAVOR ® 5.611.5 18.7 36.5 21.0 SXM-77 from Stock- hausen

As can be seen, each prior art superabsorbent polymer exhibited a FWA at6 seconds greater than 5 g/g.

Example B

Next, various selected particle size distributions of Stockhausen'sFAVOR® SXM-77 were tested for FWA at 23° C. at 750 rpm agitation speed.The results are summarized below in Table IB.

TABLE IB Particle Size (in Particle Size (in U.S. 15 seconds FWAmicrometers) standard meshes) (g/g)  44 to 841  −20/+325 10.9 595 to 841−20/+30 5.5 420 to 595 −30/+40 7.3 297 to 420 −40/+50 12.6 149 to 297 −50/+100 26.1  88 to 149 −100/+170 53.6 44 to 88 −170/+325 73.3

As can be seen, only the largest particle size distribution (595 to 841micrometers) of superabsorbent SXM-77 exhibited a slow and low FWA at 15seconds of 5.5 g/g, which is in keeping with, as noted above, theinverse relationship that as the particle size increased, then the FWAdecreased.

In contrast, as discussed in more detail below in Laboratory Examples IIA through H vis-a-vis superabsorbent polymers according to the presentinvention, the full particle size distribution of 90 to 850 micrometersfor these superabsorbent polymers typically exhibited a FWA at 15seconds of 4.0 g/g or less, and only one sample of this full particlesize distribution exhibited a FWA at 15 seconds of 6.4 g/g.

II. Examples A through H (of SAPs of Present Invention) and ComparisonExamples A and B (of SAPs without Treatment of Two-Part Thermal Profile)

In the following examples, each superabsorbent polymer was across-linked sodium polyacrylate made by solvent polymerization. Also,each percentage recited was a weight %, unless specifically indicatedotherwise as a mol %, and the aqueous ethylene carbonate was a solutionof 50 parts by weight of ethylene carbonate and 50 parts by weight ofdeionized water.

Example A

An aqueous acrylic acid solution comprising 0.1% EO-TMPTA as across-linking agent, 0.25% AII-PEGMA as a co-cross-linking agent, and2.5% methoxy polyethylene glycol methacrylate, all relative to acrylicacid, was neutralized with sodium hydroxide solution under cooling. Theacrylic acid concentration of the monomer solution amounted to 29%, witha neutralization degree of 70 mol %.

The monomer solution was cooled to about 5° C., purged with nitrogen,and then mixed with sodium erythobate solution as a reducing agent,hydrogen peroxide solution as an oxidant, (the sodium erythobate forminga redox initiator couple with the hydrogen peroxide), sodium carbonatesolution as a foaming agent to generate a porous polymer gel, and afourth solution containing both ABAH and sodium persulfate as thermalinitiators which generate free radicals throughout the course of thereaction to complete the polymerization The final concentration of eachof sodium erythobate, hydrogen peroxide, sodium carbonate, ABAH, andsodium persulfate was respectively at 57, 125, 600, 125, and 100 ppm,all relative to total monomer solution.

Polymerization started immediately after the monomer solution was mixedwith all other solutions. After 20 minutes of polymerization, the formedpolymer gel was crumbled and dried in hot air at 150° C. for 20 minutes.

The dried polymer was subsequently ground, screened to 90 to 850micrometers and continuously fed into a paddle mixer (380 rpm) at 4000kg/hour while mixing with aqueous ethylene carbonate at a 1:167 ratio byweight of ethylene carbonate to polymer in order to coat this surfacecross-linking agent onto the polymer.

The mixture was then transferred to a conveyor where it was heated froma beginning temperature of 65° C. to a final temperature of 185° C.within 1 hour for the first part of the thermal profile. Subsequently,the mixture was rapidly brought to 200° C. and maintained at thatconstant temperature of 200° C. for an additional 45 minutes for thesecond part of the thermal profile. After cooling, the resultant productwas transported to a storage vessel.

Example B

The same procedure as described in Example A was used except that forthe second part of the thermal profile, the mixture was maintained for35 minutes at a constant temperature of 210° C. after thepolymer/ethylene carbonate mixture had been heated for the first part ofthe thermal profile to a final temperature of 185° C. The resultantproduct was transported to a storage vessel after cooling.

Example C

The same procedure as described in Example A was used except that forthe second part of the thermal profile, the mixture was maintained for50 minutes at a constant temperature of 205° C. after thepolymer/ethylene carbonate mixture had been heated for the first part ofthe thermal profile to a final temperature of 185° C. The resultantproduct was transported to a storage vessel after cooling.

Example D

An aqueous acrylic acid solution comprising 0.19% triallyl amine as across-linking agent, relative to acrylic acid, was neutralized withsodium hydroxide solution under cooling. The acrylic acid concentrationof the monomer solution amounted to 31%, with a neutralization degree of70 mol %.

The monomer solution was cooled to about 5° C., purged with nitrogen,and then mixed with sodium erythobate solution as a reducing agent,t-butyl hydrogen peroxide solution as an oxidant, (the sodium erythobateforming a redox initiator couple with the t-butyl hydrogen peroxide),and a third solution containing both ABAH and sodium persulfate asthermal initiators which generate free radicals throughout the course ofthe reaction to complete the polymerization. The final concentration ofeach of sodium erythobate, t-butyl hydrogen peroxide, ABAH, and sodiumpersulfate was respectively at 26, 182, 195, and 100 ppm, all relativeto total monomer solution.

Polymerization started immediately after the monomer solution was mixedwith all other solutions. After 20 minutes of polymerization, the formedpolymer gel was crumbled and dried in hot air at 150° C. for 20 minutes.

The dried polymer was subsequently ground, screened to 90 to 850micrometers and continuously fed into a paddle mixer (380 rpm) at 4000kg/hour while mixing with aqueous ethylene carbonate as a surfacecross-linking agent at a 1:167 ratio by weight of ethylene carbonate topolymer in order to coat this surface cross-linking agent onto thepolymer.

The mixture was then transferred to a conveyor where it was heated froma beginning temperature of 80° C. to a final temperature of 170° C.within 1 hour for the first part of the thermal profile. Subsequently,the mixture was maintained at a constant temperature of 200° C. for anadditional 60 minutes for the second part of the thermal profile. Aftercooling, the resultant product was transported to a storage vessel.

Example E

The same procedure as described in Example D was used except that forthe second part of the thermal profile, the mixture was maintained foran additional 60 minutes at a constant temperature of 205° C., after thepolymer/ethylene carbonate mixture had been heated to the finaltemperature of 170° C. for the first part of the thermal profile. Theresultant product was transported to a storage vessel.

Example F

The same procedure as described in Example D was used except that forthe second part of the thermal profile, the mixture was maintained foran additional 45 minutes at a constant temperature of 210° C. after thepolymer/ethylene carbonate mixture had been heated to the finaltemperature of 170° C. for the first part of the thermal profile. Theresultant product was transported to a storage vessel after cooling.

Example G

An aqueous acrylic acid solution comprising 0.19% triallyl amine as across-linking agent, relative to acrylic acid, was neutralized withsodium hydroxide solution under cooling. The acrylic acid concentrationof the monomer solution amounted to 31%, with a neutralization degree of60 mol %.

The monomer solution was cooled to about 5° C., purged with nitrogen,and then mixed with ascorbic acid solution as a reducing agent, t-butylhydrogen peroxide solution as an oxidant, (the ascorbic acid forming aredox initiator couple with the t-butyl hydrogen peroxide), and a thirdsolution containing both ABAH and sodium persulfate. The finalconcentration of each of ascorbic acid, t-butyl hydrogen peroxide, ABAH,and sodium persulfate was respectively at 22, 178, 200, and 100 ppm, allrelative to total monomer solution.

Polymerization started immediately after the monomer solution was mixedwith all other solutions. After 20 minutes of polymerization, the formedpolymer gel was crumbled and dried in hot air at 150° C. for 20 minutes.

The dried polymer was subsequently ground, screened to 90 to 850micrometers and continuously fed into a paddle mixer (380 rpm) at 4000kg/hour while mixing with aqueous ethylene carbonate as a surfacecross-linking agent, at a 1:206 ratio by weight of ethylene carbonate topolymer in order to coat this surface cross-linking agent onto thepolymer.

The mixture was then transferred to a conveyor where it was heated froma beginning temperature of 80° C. to a final temperature of 175° C.within 1 hour for the first part of the thermal profile. Subsequently,the mixture was maintained at a constant temperature of 180° C. for anadditional 45 minutes for the second part of the thermal profile. Aftercooling, the resultant product was transported to a storage vessel.

Example H

The same procedure as describe in Example G was used except that for thesecond part of the thermal profile, the mixture was maintained for anadditional 35 minutes at a constant temperature of 190° C. after thepolymer/ethylene carbonate mixture had been heated to the finaltemperature of 175° C. The resultant product was transported to astorage vessel after cooling.

Comparison Example A (with only First Part of Two-part Thermal Profile)

The polymer prepared as described in Example E was dried, ground,screened to 90 to 850 micrometers, and continuously fed into a paddlemixer (380 rpm) at 4000 kg/hour while mixing with ethylene carbonate asa surface cross-linking agent at a 1:167 ratio by weight of ethylenecarbonate to polymer in order to coat this surface cross-linking agentonto the polymer.

The mixture was then transferred to a conveyor where it was heated froma beginning temperature of 80° C. to a final temperature of 175° C.within 1 hour as the first part of the thermal profile, and then aftercooling, the resultant product was transferred to a storage vessel. Thesecond part of the thermal profile was not performed.

Comparison Example B (with only Second Part of Two-part Thermal Profile)

The polymer prepared as described in Example E was dried, ground,screened to 90 to 850 micrometers, and continuously fed into a paddlemixer (380 rpm) at 4000 kg/hour while mixing with ethylene carbonate ata 1:167 ratio by weight of ethylene carbonate to polymer in order tocoat this surface cross-linking agent onto the polymer.

The mixture was then transferred to a conveyor where it was heated at aconstant temperature of 205° C. for 2 hours for the second part of thethermal profile. The resultant product was cooled and transported to astorage vessel. The first part of the thermal profile was not performed.

The resultant superabsorbent polymers of Examples A through H andComparison Examples A and B were tested for FWA, CRC, and AUL. For theFWA test, the particle size distribution was the full 90 to 850micrometers. However, for the CRC test and the AUL test, the polymerswere sieved, and hence, the particle size distribution was theabove-noted 300 to 600 micrometers. The FWA test was conducted withwater, whereas each of the CRC test and the AUL test was conducted with9% by weight aqueous saline. The results are summarized below in TableII.

TABLE II Example 6 15 30 of seconds seconds seconds CRC AUL SAP FWA(g/g) FWA (g/g) FWA (g/g) (g/g) (g/g) Ex. A 2.6 6.4 18.8 33.5 19.2 Ex. B1.9 4.0 14.0 30.3 21.6 Ex. C 1.3 3.0 11.3 28.4 19.7 Ex. D 0.9 2.8 10.033.0 15.6 Ex. E 1.1 2.4 9.3 35.3 13.7 Ex. F 1.2 2.7 8.3 31.9 14.7 Ex. G1.5 3.3 9.7 30.0 18.2 Ex. H 1.6 3.6 10.2 29.4 20.3 Compari- 5.7 13.522.4 38.3 11.5 son A Compari- 3.8 11.4 35.2 37.9 10.0 son B

As can be seen, for the inventive superabsorbent polymers that had beensubjected to the two-part thermal profile, each exhibited a FWA at 6seconds less than 3 g/g, and most exhibited a FWA at 6 seconds less than2 g/g. On the other hand, for the two comparisons that had beensubjected to only one of the two parts of the thermal profile, eachexhibited a FWA at 6 seconds greater than 3.5 g/g. Moreover, each of thesuperabsorbent polymers that had been subjected to the two-part thermalprofile exhibited a far superior AUL, as compared to the AUL of each ofthe two comparisons.

III. Examples of Web of SAP and Cellulosic Fluff made by Wet-LaidProcess

In the following examples, selected inventive SAPs and also the twocomparison SAPs, made as described above in Example II, were eachrespectively employed in a wet-laid process to make a wet-laid web ofSAP and cellulosic fiber.

More specifically, 1.36 grams of cellulosic fiber (GOLDEN ISLES® 4800sold by Georgia Pacific) was added to 200 grams of tap water, and then,0.9 gram of the selected SAP was added. The resultant slurry was thenpoured into a laboratory web molder having a 150 micrometer polyesterscreen at the bottom.

The web molder was made with a stainless steel, sampling chamber on thetop for retaining the slurry. The chamber measured 8.5 cm in diameterand 10 cm in height. Also, the web molder had a bottom section that wasconnected through a ball valve to a vacuum system.

The slurry was agitated with a 3-blade fan-shaped turbine agitatormoving in an up-and-down fashion for 5 times. The water temperature wascontrolled at 23° C.±1° C., and the total water contact time of the SAPand cellulosic fiber mixture was controlled to be 10 seconds. Next, thewater was drained under vacuum (60 mm Hg) from the slurry, with adraining time of 60 seconds.

The solids content of each respective web was determined according tothe following equation:Solids wt %=[(fiber wt+SAP wt)/web wt]×100%where each wt (i.e., the weight of fiber, the weight of SAP, and theweight of web) was in grams. The results are summarized below in TableIII.

TABLE III SAP/Cellulosic Fiber Web Solids Content Example of SAP Ratio(weight/weight) (weight %) none 0/100 23.9 Example A 40/60 18.1 ExampleC 40/60 21.6 Example D 40/60 22.1 Example E 40/60 23.9 Example F 40/6023.0 Example H 40/60 22.1 Comparison A 40/60 16.3 Comparison B 40/6017.7

As can be seen from the above Table III, wet-laid webs made with theinventive SAPs (Examples A, C, D, E, F, and H) exhibited an improvedsolids content versus wet-laid webs made with the comparison SAPs(Comparison Examples A and B). More specifically, the solids content foreach of the wet-laid webs made with the inventive SAPs was always above18%, whereas the solids content for each of the wet-laid webs made withthe comparison SAPs was always below 18%.

It will be understood that various details of the invention may bechanged without departing from the scope of the invention. Furthermore,the foregoing description is for the purpose of illustration only, andnot for the purpose of limitation—the invention being defined by theclaims.

1. A wet-laid web comprising a fibrous component and a superabsorbentpolymer component, wherein: (a) the superabsorbent polymer comprises adelayed absorption, particulate superabsorbent polymer having a freewater absorption property of absorbing less than about 3 grams of waterper gram of superabsorbent polymer in about 6 seconds, for a fullparticle size distribution ranging from about 40 micrometers to about890 micrometers; and (b) the weight ratio of the superabsorbent polymercomponent to the fibrous component is controlled to be in a range fromabout 90:10 to about 5:95.
 2. The wet-laid web of claim 1, wherein thesuperabsorbent polymer has a free water absorption property of absorbingless than about 7 grams of water per gram of superabsorbent polymer inabout 15 second, for a full particle size distribution ranging fromabout 40 micrometers to about 890 micrometers.
 3. The wet-laid web ofclaim 1, wherein the superabsorbent polymer has a centrifuge retentioncapacity property of retaining more than 28 grams of aqueous saline pergram of superabsorbent polymer.
 4. The wet-laid web of claim 1, whereinthe superabsorbent polymer has an absorbency under load property at 0.9psi (60 g/cm²) of retaining more than 13 grams of aqueous saline pergram of superabsorbent polymer.
 5. The wet-laid web of claim 1, whereinthe superabsorbent polymer is surface cross-linked.
 6. A method forimproving the solids content of a wet-laid web having a fibrouscomponent and a superabsorbent polymer component, said methodcomprising: (a) preparing a particulate superabsorbent polymer; (b)forming the superabsorbent polymer component by subjecting theparticulate superabsorbent of step (a) to a thermal profile having afirst part and a second part, wherein the first part comprising heatingthe superabsorbent polymer with an increasing temperature from abeginning temperature to a final increased temperature and the secondpart comprises maintaining heating of the superabsorbent polymer at aconstant temperature that is at least about 5° C. higher than the finalincreased temperature of the first part, and wherein the temperaturesand the times for heating of each of the first part and the second partare sufficient to achieve a delayed absorption, particulatesuperabsorbent polymer having a free water absorption property ofabsorbing less than about 3 grams of aqueous saline per gram ofsuperabsorbent polymer in about 6 seconds, for a full particle sizedistribution ranging from about 40 micrometers to about 890 micrometers;(c) forming en aqueous suspension of the fibrous component together withthe superabsorbent polymer component from step (b); and (d) drying thesuspension from step (c) to achieve a wet-laid web having an improvedsolids content.
 7. The method of claim 6, wherein the constanttemperature for maintaining the heating in the second part is a constanttemperature from about 5° C. to about 50° C. higher than the finalincreased temperature of the first part.
 8. The method of claim 6,wherein the temperature of the first part increases from a beginningtemperature between about 50° C. and about 80° C. to a final increasedtemperature between about 170° C. and about 220° C., and the constanttemperature in the second part is between about 175° C. and about 270 C.
 9. The method of claim 6, wherein the time for the heating of thefirst part ranges from about 30 minutes to about 90 minutes.
 10. Themethod of claim 6, wherein the time for the heating of the second partranges from about 30minutes to about 90 minutes.
 11. The method of claim6, wherein the superabsorbent polymer has a free water absorptionproperty of absorbing less than about 6 grams of water per gram ofsuperabsorbent polymer in about 15 seconds, for a full particle sizedistribution ranging from about 40 micrometers to about 890 micrometers.12. The method of claim 6, wherein the superabsorbent polymer has acentrifuge retention capacity property retaining more than 28 grams ofaqueous saline per gram of superabsorbent polymer.
 13. The method ofclaim 6, wherein the superabsorbent polymer has an absorbency under loadproperty of retaining more than 13 grams at aqueous saline per gram ofsuperabsorbent polymer.
 14. The method of claim 6, wherein step (a)includes a coating treatment with a surface cross-linking agent and step(b) is performed after the coating treatment.
 15. The method of claim 6,wherein the resultant wet-laid web has an improved solids content aboveabout 16 weight %.